KR20140006826A - Resin composition, and printed wiring board, laminated sheet, and prepreg using same - Google Patents

Abstract

The present invention provides a resin composition containing (a) a maleimide compound having at least two N-substituted maleimide groups in one molecular structure, and (b) a silicone compound having at least one reactive organic group in one molecular structure, and using the same A prepreg, a laminated board, and a printed wiring board are related. This invention can provide the resin composition excellent in heat resistance and low thermal expansion, the prepreg, laminated board, and printed wiring board using the same.

Description

Resin composition and prepreg, laminated board, printed wiring board using the same {RESIN COMPOSITION, AND PRINTED WIRING BOARD, LAMINATED SHEET, AND PREPREG USING SAME}

TECHNICAL FIELD The present invention relates to a resin composition which has insulation, heat resistance, and the like, and is particularly excellent in low thermal expansion and is used for an electronic component, a prepreg, a laminated board, and a printed wiring board using the same.

BACKGROUND With the recent trend of miniaturization and high performance of electronic devices, advancement and high integration of wiring density have progressed in printed wiring boards, and with this, there is a strong demand for improved reliability by improving heat resistance of wiring laminates. In such a use, it is desired to have excellent heat resistance and a low linear expansion coefficient.

As a laminated board for printed wiring boards, it is common to harden | cure and integrally shape the resin composition and glass woven fabric which made epoxy resin the main agent. In general, epoxy resins have excellent balance of insulation, heat resistance, cost, etc., but in order to respond to requests for improvement in heat resistance due to high density mounting and high multilayer structure of recent printed wiring boards, there is no limit to the increase in heat resistance. have. Moreover, since thermal expansion coefficient is large, low thermal expansion is aimed at by high filling of inorganic fillers, such as selection of the epoxy resin which has an aromatic ring, and silica, etc. (for example, refer patent document 1).

In recent years, in semiconductor package substrates, the warpage caused by the difference in the coefficient of thermal expansion between the chip and the substrate has become a major problem in miniaturization and thinning, and at the time of component mounting or package assembly, a low thermal expansion is required. Increasing the filling amount of the filler is known to cause lowering of insulation reliability due to moisture absorption, insufficient adhesion of the resin-wiring layer, and poor press molding.

In addition, polybismaleimide resins widely used in high-density packaging and high-layered laminates have excellent heat resistance, but have high hygroscopicity and have difficulty in adhesion. Moreover, compared with an epoxy resin at the time of lamination | stacking, it requires the high temperature and long time, and there exists a fault that productivity is bad.

That is, in general, the epoxy resin can be cured at a temperature of 180 ° C. or lower, but when laminating polybismaleimide resin, a long time treatment is required at a high temperature of 220 ° C. or higher. In addition, the modified imide resin composition has improved moisture resistance and adhesion (see Patent Document 2, for example), but is modified with a low molecular compound containing a hydroxyl group and an epoxy group in order to ensure solubility in a universal solvent such as methyl ethyl ketone. Therefore, the heat resistance of the modified imide resin obtained is significantly inferior to that of the polybismaleimide resin.

Japanese Patent Publication No. 5-148343 Japanese Patent Laid-Open No. 6-263843

In view of such a reality, an object of the present invention is to provide a resin composition excellent in heat resistance and low thermal expansion, and a prepreg, a laminated board, and a printed wiring board using the same.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, the present inventors discovered that the resin composition containing a polybismaleimide resin and the silicone resin which has a reactive organic group meets the said objective.

That is, this invention provides the following resin composition, a prepreg laminated board, and a printed wiring board.

1. (a) The resin composition containing the maleimide compound which has at least 2 N-substituted maleimide group in 1 molecular structure, and (b) the silicone compound which has at least 1 reactive organic group in 1 molecular structure.

2. (c) The resin composition of 1 above which further contains a thermosetting resin.

3. (d) The resin composition as described in said 1 or 2 which further contains the amine compound which has an acidic substituent represented by following General formula (I).

(In formula, when there exists a plurality, R <_1> , respectively independently represents a hydroxyl group, a carboxyl group, or a sulfonic acid group which is an acidic substituent, and when there are _two or more, R <_2> represents a hydrogen atom, a C1-C5 aliphatic hydrocarbon group, or a halogen atom each independently. , x is an integer of 1 to 5, y is an integer of 0 to 4, x + y = 5)

4. Resin composition in any one of said 1-3 whose component (b) is a silicone compound containing the structure represented by following General formula (II).

[Wherein, R ₃ and R ₄ each independently represent an alkyl group, a phenyl group or a substituted phenyl group, and n is an integer of 1 to 100]

5. Resin composition in any one of said 1-4 whose reactive organic group of (b) component is at least 1 sort (s) chosen from an epoxy group, an amino group, a hydroxyl group, a methacryl group, a mercapto group, a carboxyl group, and an alkoxy group.

6. Resin composition in any one of said 1-5 whose (b) component is silicone compound which has at least 2 reactive organic group in 1 molecular structure.

7. The resin composition according to any one of the above 1 to 5, wherein the component (b) is a silicone compound having a reactive organic group at both terminals.

8. (b) The resin composition in any one of said 1-5 whose component is a silicone compound which has a reactive organic group in either terminal.

9. (b) The resin composition in any one of said 1-5 whose component is a silicone compound which has a reactive organic group in a side chain.

10. The resin composition as described in any one of said 1-5 whose (b) component is a silicone compound which has a side chain and a reactive organic group in at least one terminal.

11. The resin composition according to any one of the above 1 to 10, wherein the component (c) is a thermosetting resin having an epoxy group and / or a cyanate group in its molecular structure.

12. The resin composition as described in any one of said 1-11 which further contains the (e) hardening accelerator represented by following General formula (III) or (IV).

(In formula, R <_6> , R <_7> , R <_8> , R <_9> respectively independently represents a hydrogen atom, a C1-C5 aliphatic hydrocarbon group, or a phenyl group, and D is an alkylene group or an aromatic hydrocarbon group.)

(In formula, R <_6> , R <_7> , R <_8> , R <_9> respectively independently represents a hydrogen atom or a C1-C5 aliphatic hydrocarbon group and a phenyl group, B is a single bond or an alkylene group, an alkylidene group, and an ether Group, sulfonyl group)

13. (f) The resin composition as described in any one of said 1-12 which further contains an inorganic filler.

14. Prepreg using the resin composition in any one of said 1-13.

15. The laminated board obtained by carrying out lamination | molding using the prepreg of 14.

16. The printed wiring board manufactured using the laminated board of 15.

The prepreg obtained by impregnating or coating the resin composition of the present invention into a substrate, the laminated board produced by laminating the prepreg, and the multilayer printed wiring board manufactured using the laminated board have a glass transition temperature, thermal expansion coefficient, and solder heat resistance. It is excellent in bending property and is useful as a printed wiring board for electronic devices.

Hereinafter, the present invention will be described in detail. This invention is a resin composition characterized by containing (a) the maleimide compound which has at least 2 N-substituted maleimide group in 1 molecular structure, and (b) the silicone compound which has at least 1 reactive organic group in 1 molecular structure. to be.

As a maleimide compound which has at least 2 N-substituted maleimide group in 1 molecule of (a) component in the resin composition of this invention, it is N, N'-ethylenebismaleimide, N, N'-hexamethylene, for example. Bismaleimide, N, N '-(1,3-phenylene) bismaleimide, N, N'-[1,3- (2-methylphenylene)] bismaleimide, N, N '-[1, 3- (4-methylphenylene)] bismaleimide, N, N '-(1,4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimido Phenyl) methane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, bis ( 4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (Maleimidomethyl) cyclohexane, 1,4-bis (maleimidomethyl) benzene, 1,3-bis (4-maleimidophenoxy) bene , 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4- (4-maleimidophenoxy) phenyl] methane, 1, 1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleic Midodophenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2, 2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-maleic Midodophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [ 4- (4-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimidophenoxy) biphenyl, 4,4- Bis (4-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, 2,2-bis (4-maleimidophenyl) disulfide, bis (4-maleimidophenyl) disulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) Phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy ) Phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl ] Ether, 1,4-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -α, α- Dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4- Maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3- Maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl ] Benzene, polyphenylmethane maleimide (for example, Daiwa Kasei Co., Ltd. make, brand name: BMI-2300, etc.), These maleimide compounds may be used independently, or may be used in mixture of 2 or more types. .

Among these maleimide compounds, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, N, N '-(1,3-phenylene) bismalee, which have a high reaction rate and are capable of higher heat resistance Mid, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane and polyphenylmethanemaleimide are preferable, and bis (4-maleimidophenyl) methane is particularly preferable in view of solubility in solvents. Do.

As a silicone compound which has at least 1 reactive organic group in 1 molecular structure of (b) component, there exists a silicone compound containing the structure represented by following General formula (II).

[Wherein, R ₃ and R ₄ each independently represent an alkyl group, a phenyl group or a substituted phenyl group, and n is an integer of 1 to 100]

As the component (b), a silicone compound having at least two reactive organic groups in one molecular structure is preferably used, a silicone compound having a reactive organic group at both ends of the silicone structure as described above, and a silicone compound having a reactive organic group at either end In addition, the silicone compound which has a reactive organic group in a side chain, and the silicone compound which has a reactive organic group in a side chain and at least one terminal is used.

Examples of the reactive organic group in the silicone compound having at least one reactive organic group in one molecular structure of the component (b) include an epoxy group, an amino group, a hydroxyl group, a methacryl group, a mercapto group, a carboxyl group, and an alkoxy group.

A commercial item can be used for the silicone compound which has an epoxy group in a molecular structure, For example, "X-22-163" (functional group equivalent 200), "KF-105" (functional group equivalent 490), and "X" which have an epoxy group in the both terminal. -22-163A "(functional equivalent 1000)," X-22-163B "(functional equivalent 1750)," X-22-163C "(functional equivalent 2700)," X-22- which has an alicyclic epoxy group at both ends. 169AS "(functional group equivalent 500)," X-22-169B "(functional group equivalent 1700)," X-22-1730X "(functional group equivalent 4500) which has an epoxy group in one terminal," X which has an epoxy group in a side chain and both ends -22-9002 "(functional equivalent 5000)," X-22-343 "(functional equivalent 525), epoxy group in a side chain," KF-101 "(functional equivalent 350)," KF-1001 "(functional equivalent 3500) "X-22-2000" (functional equivalent 620), "X-22-4741" (functional equivalent 2500), "KF-1002" (functional equivalent 4300), "X-22- which has alicyclic epoxy group in a side chain 2046 '' (functional equivalent 600), "KF-102, and (a functional group equivalent 3600, Shin-Etsu least Kogyo (Co., Ltd.) Chemical) be mentioned, which may be used either individually or in combination of two or more thereof, in combination with further various epoxy resins.

Among the silicone compounds having an epoxy group in these molecular structures, "X-22-163A", "X-22-163B", "X-22-343", "X-22-9002" and "KF-101" in terms of heat resistance. "," X-22-163A "and" X-22-163B "are more preferable, and" X-22-163B "is especially preferable at the point of low thermal expansion coefficient.

The commercially available silicone compound which has an amino group in a molecular structure can be used, for example, "KF-8010" (functional group equivalent 430), "X-22-161A" (functional group equivalent 800), and "X" which have an amino group in both terminal. -22-161B "(functional equivalent 1500)," KF-8012 "(functional equivalent 2200)," KF-8008 "(functional equivalent 5700)," X-22-9409 "(functional equivalent 700)," X-22 -1660B-3 '' (functional group equivalent 2200) (above, Shin-Etsu Chemical Co., Ltd. product), `` BY-16-853U '' (functional group equivalent 460), `` BY-16-853 '' (functional group equivalent 650), `` BY-16-853B '' (functional group equivalent 2200) (above, Toray Dow Corning Co., Ltd.), `` KF-868 '' (functional group equivalent 8800) having amino group in side chain, "KF-865" (functional group equivalent 5000) And `` KF-864 '' (functional equivalent 3800), `` KF-880 '' (functional equivalent 1800), `` KF-8004 '' (functional equivalent 1500) (above, manufactured by Shin-Etsu Chemical Co., Ltd.) These may be used alone or in combination of two or more thereof. It is possible.

Among the silicone compounds having an amino group in these molecular structures, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3 and BY-16-853B are preferable in view of low water absorption. In addition, X-22-161A, X-22-161B, and KF-8012 are particularly preferable in terms of low thermal expansion.

The commercially available silicone compound which has a hydroxyl group in a molecular structure can be used, for example, "KF-6001" (functional group equivalent 900), "KF-6002" (functional group equivalent 1600) which have a hydroxyl group at both ends, and a phenol at both ends. `` X-22-1821 '' (functional group equivalent 1470) (above, Shin-Etsu Chemical Co., Ltd. make), `` BY-16-752A '' (functional group equivalent 1500) (above, Toray Dow Corning (note Production), "X-22-170BX" having a hydroxyl group at one end (functional group equivalent 2800), "X-22-170DX" (functional group equivalent 4670), "X-22-4039" having a hydroxyl group in a side chain (functional group Equivalent 970) "X-22-4015" (functional group equivalent 1870) (above, manufactured by Shin-Etsu Chemical Co., Ltd.) may be mentioned, and these may be used alone or in combination of two or more thereof.

The commercially available silicone compound which has a methacryl group in a molecular structure can be used, for example, "X-22-164A" (functional group equivalent 860) and "X-22-164B" (functional group equivalent 1630) which have a methacrylic group in both terminal. ) And "X-22-174DX" (functional group equivalent 4600) (above, Shin-Etsu Chemical Co., Ltd.) which has a methacryl group in one terminal, These can be used individually or in mixture of 2 or more types It may be.

A commercial item can be used for the silicone compound which has a mercapto group in molecular structure, For example, "X-22-167B" (functional group equivalent 1670) which has a mercapto group in both terminal, "KF-2001" which has a mercapto group in a side chain. (Functional group equivalent 1900) and "KF-2004" (functional group equivalent 30000) (above, Shin-Etsu Chemical Co., Ltd. product) are mentioned, These can also be used individually or in mixture of 2 or more types.

A commercial item can be used for the silicone compound which has a carboxyl group in molecular structure, For example, "X-22-162C" (functional group equivalent 2300) which has a carboxyl group in both terminal, "X-22-3710" which has a carboxyl group in one terminal. (Functional group equivalent 1450) and "X-22-3701E" (functional group equivalent 4000) which have a carboxyl group in a side chain (above, Shin-Etsu Chemical Co., Ltd. product) are mentioned, These are single or two or more types are mixed. It can also be used.

The commercially available silicone compound which has an alkoxy group in a molecular structure can be used, For example, "FZ-3704" (functional group equivalent 150) which has an alkoxy group in a side chain (above, Toray Dow Corning Co., Ltd. product) is mentioned, These are You may use individually or in mixture of 2 or more types.

1-100 mass parts is preferable with respect to 100 mass parts of (a) component, and, as for the usage-amount of (b) component, 5-80 mass parts is more preferable. By setting it as 1 mass part or more, low thermal expansion coefficient can be attained. Copper foil adhesiveness and moldability can be ensured by setting it as 100 mass parts or less.

It is preferable to contain (c) thermosetting resin further in the resin composition of this invention. Although the thermosetting resin of (c) component is not specifically limited, For example, an epoxy resin, a phenol resin, an unsaturated imide resin, a cyanate resin, an isocyanate resin, a benzoxazine resin, an oxetane resin, an amino resin, an unsaturated polyester A resin, an allyl resin, a dicyclopentadiene resin, a silicone resin, a triazine resin, and a melamine resin can be mentioned, These can also be used individually or in mixture of 2 or more types. Among them, epoxy resins and cyanate resins are preferable in view of moldability and electrical insulating properties.

Examples of the epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, and bisphenol F furnaces. Volac type epoxy resin, stilbene type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, triphenol phenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy Diglycidyl ether compounds of polycyclic aromatics such as resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, alicyclic epoxy resins, polyfunctional phenols and anthracene, and phosphorus-containing epoxy resins having phosphorus compounds introduced therein; These can also be mentioned, These can also be used individually or in mixture of 2 or more types. Among them, biphenyl aralkyl type epoxy resins and naphthalene type epoxy resins are preferable in terms of heat resistance and flame retardancy.

Moreover, as cyanate resin, bisphenol cyanate resins, such as novolak-type cyanate resin, bisphenol-A cyanate resin, bisphenol E-type cyanate resin, tetramethyl bisphenol F-type cyanate resin, and these are some tria, for example. The evolved prepolymer can be mentioned, and these can also be used individually or in mixture of 2 or more types. Of these, novolak-type cyanate resins are preferable in terms of heat resistance and flame retardancy.

10-200 mass parts is preferable with respect to 100 mass parts of (a) component, and, as for the usage-amount of (c) component, 20-100 mass parts is more preferable. By setting it as 10 mass parts or more, the outstanding moisture absorption characteristic and copper foil adhesiveness are obtained. By setting it as 200 mass parts or less, heat resistance can be ensured and low thermal expansion coefficient can be attained.

It is preferable that the resin composition of this invention contains the amine compound which has an acidic substituent represented by following General formula (I) further as (d) component.

(In formula, when there exists a plurality, R <_1> , respectively independently represents a hydroxyl group, a carboxyl group, or a sulfonic acid group which is an acidic substituent, and when there are _two or more, R <_2> represents a hydrogen atom, a C1-C5 aliphatic hydrocarbon group, or a halogen atom each independently. , x is an integer of 1 to 5, y is an integer of 0 to 4, x + y = 5)

As the amine compound of the component (d), for example, m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-aminobenzenesulfonic acid, m- Aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, and 3,5-dicarboxyaniline; among these, m-aminophenol and p-aminophenol in terms of solubility and synthesis yield , o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid and 3,5-dihydroxyaniline are preferable, and m-aminophenol and p-aminophenol are more preferable in terms of heat resistance.

0.1-20 mass parts is preferable with respect to 100 mass parts of (a) component, and, as for the usage-amount of (d) component, 1-10 mass parts is more preferable. By setting it as 0.1 mass part or more, the outstanding heat resistance and copper foil adhesiveness are obtained. By setting it as 20 mass parts or less, heat resistance can be ensured.

It is preferable to make component (d) react with component (a) beforehand. Although the organic solvent used for this reaction is not specifically limited, For example, alcohol solvents, such as ethanol, a propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, acetone, methyl ethyl ketone, and methyl Ketone solvents such as isobutyl ketone and cyclohexanone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, methylformamide, dimethylacetamide, N-methylpyrrolidone and the like Sulfur atom containing solvents, such as a nitrogen atom containing solvent and dimethyl sulfoxide, These can also be used individually or in mixture of 2 or more types. Among them, cyclohexanone, propylene glycol monomethyl ether, and methyl cellosolve are preferable in terms of solubility, and cyclohexanone and propylene glycol monomethyl ether are more preferable in view of low toxicity. Propylene glycol monomethyl ether, which is difficult to remain as a residual solvent, is particularly preferable.

In addition, a reaction catalyst can be arbitrarily used for the said reaction as needed, and is not specifically limited. Examples of the reaction catalyst include amines such as triethylamine, pyridine and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and phosphorus catalysts such as triphenylphosphine, and these alone or two. It is also possible to use a mixture of species or more.

When making (a) component and (d) component react in an organic solvent, it is preferable that reaction temperature is 70-150 degreeC, and it is more preferable that it is 100-130 degreeC. The reaction time is preferably 0.1 to 10 hours, more preferably 1 to 6 hours.

It is preferable to use (e) a hardening accelerator for the resin composition of this invention for the improvement of heat resistance, a flame retardance, copper foil adhesiveness, etc., As an example of a hardening accelerator, imidazole, its derivatives, tertiary amines, quaternary ammonium salt, etc. are mentioned. Can be mentioned.

Among them, imidazoles and derivatives thereof are preferable from the viewpoints of heat resistance, flame retardancy, copper foil adhesiveness, and the like, and isocyanate resins represented by the following general formula (III) and imidazole groups represented by the following general formula (IV) are epoxy resins. The compound substituted by the compound substituted by the compound is more preferable because it is excellent in curing moldability at a relatively low temperature at 200 ° C. or lower and stability of varnish or prepreg, and specifically, the following formula (V) or formula ( The compound represented by VI) is particularly preferred because it can be a small amount of combined use and also commercially inexpensive.

(In formula, R <_6> , R <_7> , R <_8> , R <_9> respectively independently represents a hydrogen atom or a C1-C5 aliphatic hydrocarbon group and a phenyl group, and D is an alkylene group and an aromatic hydrocarbon group.)

(In formula, R <_6> , R <_7> , R <_8> , R <_9> respectively independently represents a hydrogen atom or a C1-C5 aliphatic hydrocarbon group and a phenyl group, B is a single bond or an alkylene group, an alkylidene group, and an ether Group, sulfonyl group)

(e) The amount of the curing accelerator used is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, more preferably 0.1 to 1 part by mass per 100 parts by mass of the total of the components (a) to (d) in terms of solid content. It is especially preferable to make it rich. When the usage-amount of a hardening accelerator is 0.1 mass part or more, the outstanding heat resistance, flame retardance, and copper foil adhesiveness will be obtained, and if it will be 10 mass parts or less, heat resistance, light stability, and press formability will not fall.

(F) Inorganic filler can be used together in the resin composition of this invention arbitrarily. As inorganic fillers, silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, potassium titanate, E Glass powder, such as glass, T glass, and D glass, hollow glass beads, etc. are mentioned, These can also be used individually or in mixture of 2 or more types.

Among the inorganic fillers of these components (f), silica is particularly preferable in terms of dielectric properties, heat resistance, and low thermal expansion. Examples of the silica include precipitated silica having a high water content, wet silica, and dry silica, which is produced by the dry method, and hardly contains any bonding water. Examples of the dry silica include crushed silica and fumed silica due to differences in production methods. And fused spherical silica. Among these, fused spherical silica is preferred from the viewpoint of low thermal expansion and high flowability when filled with a resin.

When using fused spherical silica as an inorganic filler, it is preferable that it is 0.1-10 micrometers, and, as for the average particle diameter, it is more preferable that it is 0.3-8 micrometers. By setting the average particle diameter of the molten spherical silica to 0.1 µm or more, the fluidity at the time of high filling to the resin can be maintained satisfactorily, and by setting it to 10 µm or less, the probability of incorporation of the coarse particles can be reduced to suppress the occurrence of defects caused by the coarse particles. Can be. Here, the average particle diameter refers to the particle size of the point corresponding to 50% by volume when the cumulative number distribution curve by the particle size is obtained by making the total volume of the particles 100%, and the particle size distribution measuring device using the laser diffraction scattering method. Or the like.

(f) It is preferable that it is 10-300 mass parts per 100 mass parts of total sum of (a)-(d) component of solid content conversion, and, as for content of an inorganic filler, it is more preferable that it is 50-250 mass parts. By making content of an inorganic filler into 10-300 mass parts per 100 mass parts of total resin components, the moldability and low thermal expansion property of a resin composition can be kept favorable.

In the present invention, any combination of known thermoplastic resins, elastomers, flame retardants, organic fillers and the like can be used arbitrarily within the scope not contrary to the object.

Examples of the thermoplastic resin include polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin and silicone Resin can be mentioned.

Examples of the elastomer include polybutadiene, polyacrylonitrile, epoxy modified polybutadiene, maleic anhydride modified polybutadiene, phenol modified polybutadiene and carboxy modified polyacrylonitrile.

Examples of the organic filler include organic powders such as silicon powder, tetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.

In this invention, addition of a ultraviolet absorber, antioxidant, a photoinitiator, a fluorescent whitening agent, and an adhesion improving agent can also be added arbitrarily, and is not specifically limited. Examples thereof include ultraviolet light absorbers such as benzotriazole, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals and thioxanthones, and fluorescent brighteners such as stilbene derivatives and urea. Adhesion improving agents, such as urea compounds, such as a silane, and a silane coupling agent, are mentioned.

The resin composition of this invention is used as a varnish at the time of manufacturing a prepreg. The same solvent used for the said reaction is used for the solvent used for a varnish. It is preferable to use varnish as 50-75 mass% as solid content concentration.

The prepreg of this invention is formed by impregnating or coating a base material with the resin composition of this invention mentioned above. Hereinafter, the prepreg of the present invention will be described in detail.

The prepreg of this invention can be manufactured by impregnating or coating the resin composition of this invention in a base material, semi-hardening (B-stage) by heating, etc. As a base material used here, the well-known thing used for the laminated sheets for various electrical insulation materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass and Q glass, organic fibers such as polyimide, polyester and polytetrafluoroethylene, and mixtures thereof.

Although these base materials have shapes, such as a woven fabric, a nonwoven fabric, roving, a chopped strand mat, and a surface treatment mat, a material and a shape are selected according to the use and the performance of the target molding, and if needed, Alternatively, two or more kinds of materials and shapes may be combined. The thickness of the substrate is not particularly limited. For example, about 0.03 to 0.5 mm can be used, and surface treatment with a silane coupling agent or the like or mechanically open treatment is preferable in terms of heat resistance, moisture resistance, and workability. .

In the prepreg of this invention, after impregnating or coating a base material so that the adhesion amount of the resin composition with respect to the said base material may be 20-90 mass% in the resin content rate of the prepreg after drying, it is usually 1-, at the temperature of 100-200 degreeC. It can obtain by making it heat-dry for 30 minutes and semi-hardening (B stage).

The laminated board of this invention can be formed by carrying out lamination molding using the prepreg of this invention mentioned above. The prepreg of this invention can be manufactured by laminating | stacking with the structure which laminated | stacked 1-20 sheets, for example, and arrange | positioned metal foil, such as copper and aluminum, on one side or both surfaces. The metal foil is not particularly limited as long as it is used for an electrically insulating material.

The molding conditions at the time of manufacturing a laminated board can apply the method of the laminated board for electric insulation materials, and a multilayer board, for example, using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, etc., It can shape | mold in the range of temperature 100-250 degreeC, the pressure 0.2-10 MPa, and heating time 0.1-5 hours. Moreover, a laminated board can also be manufactured by combining and preforming the prepreg of this invention and the wiring board for inner layers.

The printed wiring board according to the present invention is produced by forming a circuit on the surface of the laminate. That is, the conductor layer of the laminated board which concerns on this invention is wire-processed by a normal etching method, multiple laminated | stacked laminated boards which were wire-processed through the above-prepreg, and multiply collectively by hot press work. Thereafter, a multilayer printed wiring board can be manufactured through formation of a through hole or a blind via hole by drilling or laser processing, and formation of an interlayer wiring by plating or conductive paste.

<Examples>

Next, although an Example demonstrates this invention further in detail, these Examples do not limit this invention.

Moreover, using the copper clad laminated board obtained by each Example and the comparative example, the glass transition temperature, the thermal expansion coefficient, the solder heat resistance, and the bending characteristic were measured and evaluated by the following method.

(1) Measurement of glass transition temperature (Tg)

The 5 mm square evaluation board | substrate which removed copper foil by immersing a copper clad laminated board in copper etching liquid was produced, and the thermomechanical analysis was performed by the compression method using the TMA test apparatus (TMA2940 by Dupont). After the evaluation board | substrate was attached to the said apparatus in the Z direction, it measured continuously twice in the measurement conditions of 5 g of loads and the temperature increase rate of 10 degree-C / min. Tg expressed by the intersection of different tangent lines of the thermal expansion curve in the second measurement was determined to evaluate heat resistance.

(2) Measurement of thermal expansion rate

The 5 mm square evaluation board | substrate which removed the copper foil was produced by immersing a copper clad laminated board in copper etching liquid, and the thermomechanical analysis was performed by the compression method using the TMA test apparatus (made by Dupont, TMA2940). After the evaluation board | substrate was attached to the said apparatus in the X direction, it measured continuously twice in the measurement conditions of 5 g of loads and the temperature increase rate of 10 degree-C / min. The average thermal expansion rate of 30 degreeC-100 degreeC in the 2nd measurement was computed, and made this the value of thermal expansion rate.

(3) Evaluation of Solder Heat Resistance

The copper-clad laminated board of 5 mm square was produced, the evaluation board | substrate was floated for 1 minute in the solder bath of temperature 288 degreeC, and the solder heat resistance was evaluated by observing the external appearance.

(4) Evaluation of the amount of warpage

The amount of warpage of the substrate was evaluated using a Thermoray PS200 shadow moire analysis manufactured by AKROMETRIX. The sample size of the board | substrate was 40 mm x 40 mm, and the measurement area was 36 mm x 36 mm. The amount of warpage at the time of heating from room temperature to 260 degreeC and cooling to 50 degreeC after that was measured.

Examples 1 to 18, Comparative Examples 1 to 3

By using methyl ethyl ketone for the components (a) to (d) shown below, (e) a curing accelerator, (f) an inorganic filler, and a diluting solvent, at a blending ratio (mass parts) shown in Tables 1 to 5 It mixed and obtained the uniform varnish of 65 mass% of resin powders.

Next, the varnish was impregnated and coated with E glass cloth having a thickness of 0.1 mm, and heated and dried at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 50% by mass.

Four prepregs were superimposed, 18 micrometers electrolytic copper foil was arrange | positioned up and down, and it pressed for 90 minutes at the pressure of 2.5 MPa, and temperature of 230 degreeC, and obtained the copper clad laminated board.

The measurement and evaluation results of the obtained copper clad laminate are shown in Tables 1 to 5.

(a) maleimide compounds

Bis (4-maleimidophenyl) methane

3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide

(b) silicone compounds

X-22-161A (Shin-Etsu Chemical Co., Ltd. make, both terminal amino denaturation, functional group equivalent 800)

X-22-161B (Shin-Etsu Chemical Co., Ltd. make, both terminal amino denaturation, functional group equivalent 1500)

KF-8012 (manufactured by Shin-Etsu Chemical Co., Ltd., both terminal amino modifications, functional group equivalent 2200)

KF-864 (manufactured by Shin-Etsu Chemical Co., Ltd., one terminal amino modification, functional group equivalent 3800)

X-22-163B (Shin-Etsu Chemical Co., Ltd. make, both terminal epoxy modification, functional group equivalent 1750)

KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd., both ends hydroxyl group modification, functional group equivalent 1600)

X-22-1821 (Shin-Etsu Chemical Co., Ltd. make, both terminal phenolic hydroxyl group modification, functional group equivalent 1470)

X-22-164A (Shin-Etsu Chemical Co., Ltd. make, both terminal methacryl modification, functional group equivalent 860)

X-22-167B (Shin-Etsu Chemical Co., Ltd. make, both terminal mercapto denaturation, functional group equivalent 1670)

X-22-162C (Shin-Etsu Chemical Co., Ltd. make, both terminal carboxyl modification, functional group equivalent 2300)

FZ-3704 (Toray Dow Corning Co., Ltd. side chain alkoxy modification, functional group equivalent 150)

(c) thermosetting resin

Biphenyl aralkyl type epoxy resin (NC-3000 by Nippon Kayaku Co., Ltd.)

Bisphenol A type cyanate resin (Lonza Japan Co., Ltd. make B10)

(d) amine compounds

m-Aminophenol

p-aminophenol

(e) Curing accelerators:

G-8,009L (Addition reactant of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole: the compound represented by said Formula (V).)

(f) Inorganic filler: Fused silica (SO-C2 manufactured by Admatex)

Other compounds

Diaminodiphenylmethane (comparative example)

2,2-bis [4- (aminophenoxy) phenyl] propane (comparative example)

As is clear from Tables 1 to 5, the Examples of the present invention are excellent in glass transition temperature, thermal expansion coefficient, solder heat resistance, and warpage characteristics. On the other hand, the comparative example is inferior in any one of the characteristics in the glass transition temperature, thermal expansion coefficient, solder heat resistance, and curvature characteristic.

The multilayer printed wiring board manufactured using the laminated board manufactured by laminating | molding the prepreg obtained from the thermosetting resin composition of this invention is excellent in glass transition temperature, a thermal expansion coefficient, solder heat resistance, and a bending characteristic, and was highly integrated printed wiring board for electronic devices. It is useful as.

Claims (16)

A resin composition comprising (a) a maleimide compound having at least two N-substituted maleimide groups in one molecular structure, and (b) a silicone compound having at least one reactive organic group in one molecular structure. The resin composition of Claim 1 which further contains (c) thermosetting resin. (D) The resin composition of Claim 1 or 2 which further contains the amine compound which has an acidic substituent represented by following General formula (I).

(In formula, when there exists a plurality, R <_1> , respectively independently represents a hydroxyl group, a carboxyl group, or a sulfonic acid group which is an acidic substituent, and when there are _two or more, R <_2> represents a hydrogen atom, a C1-C5 aliphatic hydrocarbon group, or a halogen atom each independently. , x is an integer of 1 to 5, y is an integer of 0 to 4, x + y = 5) The resin composition of any one of Claims 1-3 whose component (b) is a silicone compound containing the structure represented by following General formula (II).

[Wherein, R ₃ and R ₄ each independently represent an alkyl group, a phenyl group or a substituted phenyl group, and n is an integer of 1 to 100] The resin composition according to any one of claims 1 to 4, wherein the reactive organic group of the component (b) is at least one selected from an epoxy group, an amino group, a hydroxyl group, a methacryl group, a mercapto group, a carboxyl group, and an alkoxy group. The resin composition according to any one of claims 1 to 5, wherein the component (b) is a silicone compound having at least two reactive organic groups in one molecular structure. The resin composition according to any one of claims 1 to 5, wherein the component (b) is a silicone compound having a reactive organic group at both terminals. The resin composition according to any one of claims 1 to 5, wherein the component (b) is a silicone compound having a reactive organic group at either end. The resin composition according to any one of claims 1 to 5, wherein the component (b) is a silicone compound having a reactive organic group in the side chain. The resin composition of any one of Claims 1-5 whose (b) component is a silicone compound which has a reactive organic group in a side chain and at least one terminal. The resin composition according to any one of claims 1 to 10, wherein the component (c) is a thermosetting resin having an epoxy group and / or a cyanate group in its molecular structure. The resin composition of any one of Claims 1-11 which further contains the (e) hardening accelerator represented by following General formula (III) or (IV).

(In formula, R <_6> , R <_7> , R <_8> , R <_9> respectively independently represents a hydrogen atom, a C1-C5 aliphatic hydrocarbon group, or a phenyl group, and D is an alkylene group or an aromatic hydrocarbon group.)

(In formula, R <_6> , R <_7> , R <_8> , R <_9> respectively independently represents a hydrogen atom or a C1-C5 aliphatic hydrocarbon group and a phenyl group, B is a single bond or an alkylene group, an alkylidene group, and an ether Group, sulfonyl group) The resin composition according to any one of claims 1 to 12, further comprising (f) an inorganic filler. The prepreg using the resin composition of any one of Claims 1-13. The laminated board obtained by carrying out lamination | molding using the prepreg of Claim 14. The printed wiring board manufactured using the laminated board of Claim 15.